Anilide dithiolanes and dithianes

ABSTRACT

IN WHICH R IS SELECTED FROM THE GROUP CONSISTING OF ALKYL, LOWER HALOALKYL AND SUBSTITUTED PHENYL, WHEREIN SAID SUBSTIUENTS ARE SELECTED FROM THE GROUP METHYL,CHLORO AND DICHLORO; R1, R2, R3, R4, R5, R6 AND R7 EACH ARE INDEPENDENTLY SELECTED FROM THE GROUP CONSISTING OF HYDROGEN AND LOWER ALKYL; AND N IS 0 OR 1. THESE COMPOUNDS ARE USEFUL AS HERBICIDES.   R6)(-R7)-CH2)N-CH2-C(-R4)(-R5)-S-)   (3-(R-CO-NH-)PHENYL)-C(-R1)&lt;(-S-C(-R2)(-R3)-CH2-(CH2-C(-   SUBSTITUTED ANILIDE DITHIOLANE AND DITHIANE COMPOUNDS HAVING THE FORMULA

United States Patent 3,772,334 ANILIDE DITHIOLANES AND DITHIANES Eugene G. Teach, El Cerrito, Ca1if., assignor to Staulfer Chemical Company, New York, N.Y. No Drawing. Filed Oct. 26, 1971, Ser. No. 192,484 Int. Cl. C07d 71/00, 73/00 US. Cl. 260-327 M 13 Claims ABSTRACT OF THE DISCLOSURE Substituted anilide dithiolane and dithiane compounds having the formula in which R is selected from the group consisting of alkyl, lower haloalkyl and substituted phenyl, wherein said substituents are selected from the group methyl, chloro and dichloro; R R R R R R and R each are independently selected from the group consisting of hydrogen and lower alkyl; and n is 0 or 1. These compounds are useful as herbicides.

This invention relates to certain novel substituted anilide dithiolanes and dithianes which are useful as herbicides. The compounds of the present invention are new compositions of matter and correspond to the formula bodiments are intended for the various substituents: Alkyl' preferably includes, unless other wise provided for, those members which contain from 1 to 8 carbon atoms, inclusive, in both straight chain and branched chain configurations, for example, methyl, ethyl, n-propyl, isopropyl, nbutyl, isobutyl, tertiary-butyl, n-pentyl, isopentyl, neopentyl, hexyl, isohexyl, n-heptyl, iso-heptyl, n-octyl, isooctyl, 2,4,4-trimethylphentyl, and the like; lower alkyl preferably includes, unless otherwise provided for, those members which contain from 1 to 6 carbon atoms, inclusive, in both straight chain and branched chain configurations; the term halo-alkyl preferably includes, unless otherwise provided for, those members which contain as halogens fluorine or chlorine from monoto perhalogenation, including mixed halogenatio-n, such as monochloromonofluoro, dichloromonofluoro, monochlorodifiuoro and the like, as the allyl portion the preferred embdiment includes 1 t 4 carbon atoms, inclusive, for example, monochloromethyl, perfluoroethyl, monochloro-tertiary butyl and the like.

Patented Nov. 13, 1973 The compounds of this invention have been found to be active herbicides of a general type. That is, certain members of the class have been found to be herbicidally effective against a wide range of plant species. A method of controlling undesirable vegetation of the present invention comprises applying an herbicidally effective amount of the above-described compounds to the area or plant locus where control is desired.

An herbicide is used herein to mean a compound which controls or modifies the growth of plants. By a growth controlling amount is meant an amount of compound which causes a modifying effect upon the growth of plants. Such modifying effects include all deviations from natural development, for example, killing, retardation, defoliation, desiccation, regulation, stunting, tillering, stimulation, dwarfing and the like. By plants it is meant germinant seeds, emerging seedlings, and established vegetation, including the roots and above-ground portions.

The compounds of the present invention are prepared by several different methods, depending upon the nature of the starting materials and products desired. Synthesis of the starting materials can be found in several references in the literature. The following method is illustrative: Meta-nitrobenzaldehyde (wherein R supra, is hydrogen), or meta-nitroacetophenone or higher phenones (wherein R supra, is lower alkyl), are reacted with a suitable dithiol, either 1,2 or 1,3-dithiol to give the desired cyclic mercaptal. The corresponding cyclic mercaptal 1,3-dithiol is reduced by conventional methods to give the corresponding meta-amino compound. The metaamino compound is reacted with an appropriate acyl halideto obtain the desired substituted anilide dithiolane or dithiane.

Particularly, more illustrative of the above generally described method will be the following specific examples. Following the examples is a table of compounds which are prepared according to the procedures described and illustrated herein.

EXAMPLE I Preparation of intermediates 2(m-nitrophenyl)1,3-dithiane.-One hundred and sixtenths grams (100.6 g.) of m-nitro benzaldehyde, 72.4 g. of 1,3-propanedithiol and 1 g. of p-toluene sulfonic acid were combined in 200 ml. of benzene and heated to reflux under a modified Dean-Stark apparatus. The mixture was heated until no more water came off (approximately 12 ml.) and then cooled and the product crystallized. There was obtained a yield of 149 g. of the title compound, M.P. 1 12-1 14 C.

2(m-aminophenyl)1,3-dithiane.0ne hundred grams (100 g.) of iron powder was stirred with 250 ml. of ethanol and 200 ml. of water. 7 ml. of concentrated hydrochloric acid was added, and the mixture heated to reflux. One

hundred and forty-one grams (141 g.) of 2(m-nitro-- solution was removed under vacuum. There was obtained 112.8 g. of the title compound, M.P. 139-142 C.

EXAMPLE II Preparation of 2(m-propionamidophenyl)1,3-dithiane 3 :1 into water and the product collected by filtration. There was ..obtaineda. yield of. 16.6 go'.the.-.title. compound, U

M.P. 116119 C.

EXAMPLE III Preparation of intermediates 2(m-nitrophenyl)Z-methyl-1,3-dithiolane.One hundred and seventy-five grams (175 g.)-of m-nitro acetophenone, 100 g. of ethane dithiol and 1 g.'of-p-toluene'sulfonic acid were combined in 300 ml. of benzeneand heated to reflux under a modified Dean-Stark apparatus to remove water. The mixture was-heated at reflux for about 24 hours until no more water came off. The benzene was removed under vacuum in a rotary evaporator. There was obtained 257 g. of the title compound, an oil, n =1.6255. 1o

2(m-aminophenyl)2-methyl-1,3-dithiolane.--One hundred and eighty grams (180 g.) of iron powder, 375 ml. of ethyl alcohol and 300 ml. of water and 12 ml. of concentrated hydrochloric acid were stirred together and heated to reflux. Two hundred and fifty-two grams (252 g.) of

2(m-nitrophenyl)2-methyl1,3-dithio1ane was added dropwise to maintain reflux. When the addition was complete and the mixture cooled about 10, 12 g. of sodium acetone, 6.5 g. of triethylamine was added and 5.6 g. of -propionyl chloride was added portionwise with cooling.

The mixture was poured into water and the oily product taken up in methylene chloride, separated and dried over magnesium sulfate and the solvent removed under vacuum. There was obtained a yield of 13.4 g. of the title compound, n "=1 .6132.

EXAMPLE V Preparation of 2(m-2,2-dimethylvalerylamidophenyl) 2- methyl-1,3-dithiolane TABLE I R: R S-(J -CR C\ \S C/ k R1 n R R R-C-NH Compound M.P., C

umber R R1 R; R; R R; 1: R5 R1 n 1. CzHs OH: H H H H 0 1.6132 2. t-C4 0 OH; H H H H 0 124-126 3. sH1CH(CH:) OH; H H H H 0 101-103 4... CzHsCH(CH3)CHz OH; H H H H 0 64437 5. CaH1C(CHa)z CH1 H H H H 0 105-108 6. O-CHsCuHl OH; H H H H 0 86-88 7. m-C1CoH4 CH: H H H H 0 1. 6394 8. 3,5-C12CuHs CH; H H H H 0 1.6473 9.. 02115 H H H H H 1 116-119 10 C3H7CH(CH3) H H H H H 1 117-119 11 a 'I z)z H H H H H 1 126-128 CzFa H H H H H 0 83-85 13 C3H7C(CH!) H H H H H 0 90-93 14 t-C4H9CH2GH(CH;) CH1 H H H H H 0 10 hydroxide was added and the mixture filtered through a Other examples of compounds falling within the generic dicalite pad to remove excess iron and iron oxides. The 50 formula presented herein, which are preparable by the ethanol water solution was stripped to remove the ethanol and the liquid product was separated from the aqueous phase, diluted with methylene chloride, dried and the solaforedescribed procedures and which may be formulated into herbicidal compositions and applied as herein illustrated, are:

R R R2 R3 R4 R5 71 R0 R1 C2H5 CH3 CH: H H H O t-C H0 CH3 CH3 H H H 0 C:H1CH(CH;) CH3 CH3 H H H 0 C2H5 H H H H H 1 CH3 CH3 t-C4Ha H H H H H 1 CH3 CH C3H7C(CH:): H H H H H 1 CH3 CHa CzHs H CH3 CH CH3 H 1 H H CzFs H CH3 CH3 CH3 H 1 H H 02H: H CH CH CH3 CH3 0 t'Cl D H CH3 CH3 CH3 CH3 0 vent stripped off. There was obtained 197 g. of the title compound, n =1.6520.

EXAMPLE IV Preparation of 2(m-propionamidophenyl)2-methyl-1,3-

dithiolane v Twelve and seven-tenths grams (12.7 g.) of 2(m-amino- HERBICIDAL SCREENING TESTS phenyl) 2-methyl-1,3-dithiolane was dissolved in-100 ml. of 75 ner.

trol .5?

the greenho e ,treated .foilage iw th .water for h water is applied to. the soil by meansof a slow stream a t: f Oh the day preceding eed species are planted pecies per row across the Hairy crabgrass (Digiu I w oxtail (Setariaglauca( I .)fBe auv watergr s chii'tochloa crusgalli (L.) Begum), Calif i1iz 1"r ed atfy'lv ena skztiva (L.)), redroot pigweed (A'ntdranfliizs retrbflxzis (L.)), Indian mustard (Brassicrz juncea (L.) Qoss.) and curly dock (Rumex c'rispus (L.)). Ample are planted to give about 20 to 50 seedlings p'er'row, are; emergence, depending on the si ze 'oftlie plants; The flats are watered after planting. The spraying solution is "preparedby dissolving 50 mg. ofthete'stlcompound in 3' ml. ofa'solvent, such as acetone, water alcohol or dimethylforrnani'ide, containing 1% Tween 20 (polyoxyethylene So'rbitan monolaurate). whenfdimethylformamideis used, only 0.5 ml. or less is usedtodissolve the compound; Another solvent is used to make the voluiiie 'up to 3 ml. The following day after planting, each fiat is sprayed at' the rate of 20 pounds of the candidate compound per 143 gallons of solution per acre. atomizer is'used to spray the solution onto the 'soil' surface. Theflat's areplaced'in a greenhouse at 70- 85 F. and watered regularlyby sprinkling. Two weeks aftertr'eatment, the degree of weed control is determined by comparing the amount of germination and growth of each weed 'inthetreat'ed flats with 'weeds in several untreated c'ohtrohfia ts. The rating system is as follows:

=no. significant injury (approximately 0-10 percent con- 3=slight-injury (approximately 10-40 percent control) '6=moderate; :injury approximately 40-70 percent con- 9'=s evere.-.injurywor (approximately 70-100 percentcontrolj' An activityjlindex is used to. represent the total activity on jall' seven weed species The, activityindex is the sum of the numhersdivided'by '3', s o' tliat an activity index of 21 re eserits" complete control .ofal l Lseven weeds. The rehis test. are reported inTable II.

Post-emergence."herbicide test: Seeds of five weed lspecies, including'hany crabgrass, watergrass, California 'red oats" pintof bea f described are pl-a'ced in the grenhouseiatJL-SS" F. and watered Indian mustard, and curly dock and one crop, nsl.(Phase0lf "I vitlgarisfl are planted in flats as above fofr'n fp kemergen-ce screening. The flats bout'QJO to 14 days after planting,

wihen theprimary'leayes o thebean plant are almost fully expanded and the fir 'st trifoliate leaves are just starting to form the plantsare sprayed.,The spray is prepared by .fweighingout SO mgtof; the tiest compound, dissolving it in fi ml of a eet onecontaining 1 Tween 20 (polyoxyethyl- .ene sorbitan monolaurate) and then adding ml. of water.

The solution is sprayed on ,thefoliage using an atomizer. The spray concentrationl is 0.5% and the rate would be approximately 20 ,lb./acret if all "of the spray were retained on the plant .and the soil, but some sprayis lost I so it 'is. estimated that the; application rate is approximately to deteetdefoliants and plant growth Be ns are us'd regulatorsQ The beansiaretrimmer; to two or three plants .per v flat by cutting off the excess Weaker plants several days before treatmentgfThe treatedplantsare placed back in and care is taken ,to avoid sprinkling the l e days after treament.

4 screening test' is liii'Tliis index represents the sum of the rating numbers obtained with the six plant species used in the test divided by 3. The herbicide activity index is shown in Table II.

TABLE II.HE RBICIDAL ACTIVITY SCREENING RESULTS Herbicidal activity index 1 21=70100% control of all seven plant species tested pre-emelgence; 18=70l00% control of all six plant species tested post-emergence.

The compounds of the present invention are used as pro-emergence or post-emergence herbicides and are applied in a variety of ways at various concentrations. In practice, the compounds are formulated with an inert carrier, utilizing methods well-known to those skilled in the art, thereby making them suitable for application as dusts, sprays, or drenches and the like, in the form and manner required. The mixtures can be dispersed in water with the aid of a wetting agent or they can be employed in organic liquid compositions, oil and water, water in oil emulsions, with or without the addition of wetting, dispersing or emulsifying agents. An herbicidally effective amount depends upon the nature of the seeds or plants to be controlled and the rate of application varies from 1 to approximately 50 pounds per acre.

The phytotoxic compositions of this invention employing an herbicidally effective amount of the compound described herein are applied to the plants in the conventional manner. Thus, the dust and liquid compositions can be applied to the plant by the use of powder-dusters, boom and hand sprayers and spray-dusters. The compositions can also be applied from airplanes as a dust or a spray because they are effective in very low dosages. In order to modify or control growth of germinating seeds or emerging seedlings, as a typical example, the dust and liquid compositions are applied to the soil according to conventional methods and are distributed in the soil to a depth of at least /2 inch below the soil surface. It is not necessary that the phytotoxic compositions be admixed with the soil particles and these compositions can be applied merely by spraying or sprinkling the surface of the soil. The 'phytotoxic compositions of this invention can also be applied by addition to irrigation water supplied to the field to be treated. This method of application permits the penetration of the compositions into the soil as the water is absorbed therein. Dust compositions, granular compositions or liquid formulations applied to the surface of the soil can be distributed below the surface of the soil by conventional means such as discing, dragging or mixing operations.

The phytotoxic compositions of this invention can also contain other additaments, for'example, fertilizers, pesticides and the like, used as adjuvant or in combination with any of the above-described adjuvants. Other phytotoxic compounds useful in combination with the abovedescribed compounds include, for example, 2,4-dichlorophenoxyacetic acids, 2,4,5-trichlorophenoxyacetic acid, 2- methyl-4-ehlorophenoxyacetic acid and the salts, esters and amides thereof; triazine derivatives, such as 2,4-bis- (3-methoxypropylamino) 6 methyl-thio-S-triazine; 2- chloro 4 ethylamino 6 isopropylamino S triazine, and 2 ethylamino 4 isopropylamino 6 methy1mercapto S triazine, urea derivatives, such as 3-(3,4-diohlorophenyl) 1,1 dimethyl urea and 3 (p chlorophenyl) 1,1 dimethyl urea and acetamides such as N,N diallyl a chloroacetamide, N (a-chloroacetyl) hexamethylene imine, and N,N-diethyl-a-bromacetamide, and the like; benzoic acids such as 3-amino-2,5-dichloro benzoic; and thiocarbamates, such as S propyl dipropylthiocarbamate; S ethyl dipropylthiocarbamate, S-ethyldipropylthiocarbamate, S-ethylcyclohexyl-ethyl-thiocarbamate, S-ethyl hexahydro-lE-azepine-l-carbothioate and the like. [Fertilizers useful in combination with the active ingredients include, for example, ammonium nitrate, urea and superphosphate. Other useful additaments include materials in which plant organisms take root and grow, such as compost, manure, humus, sand and the like.

The concentration of a compound of the present invention, constituting an effective amount in the best mode of administration in the utility disclosed, is readily determinable by those skilled in the art.

Various changes and modifications are possible without departing from the spirit and scope of the invention described herein and will be apparent to those skilled in the art to which it pertains. It is accordingly intended that the present invention shall only be limited by the scope of the claims.

What is claimed is:

1. A compound having the formula in which R is selected from the group consisting of alkyl, lower haloalkyl and substituted phenyl, in which said substituents are selected from the group methyl, chloro and dichloro; R R R R R R and R each are independently selected fromthe group consisting of hydrogen and lower alkyl; andnisOor l.

2. A compound according to"'caim'1'in'-'which R is alkyl, R is lower alkyl, R 'R R and R are each independently hydrogen andn is 0. I

3. A compound according to 'claim'z in which R is ethyl, and R is methyl.

4. A compound "according to claim 2 tertiary-butyl and R is methyl I 5. A compound according to claim 2 in which R is l-metthylbutyl and R is methyl;-

6. A compound according'to claim' '2 'in' which 'R'is Z-methylbutyl, and R 'is methyl.

7. A compound according to claim 2 in which R is t which R is 1,1-dimethylbutyl and R is methyl. 1

8. A compound according to claim 1 in which R is lower haloalkyl, R R R R and R are each independently hydrogen. g

9. A compound according to claim 8 in whichR is pentafluoroethyl. i

10. A compound'according to claim 1 in which 'R'is alkyl, R R R R; and R are each independently hydrogen, n is 1 and R and R are each independently hydrogen. I

11. A compound according to claim 10 in which R is ethyl.

12. A compound according to claim 10 in which R is l-methylbutyl. v T

13. A compound according to claim 10 in which R is 1,1-dimethylbutyl.

References Cited I UNITED .sTATEs PATENTS 3,461,137 8/1969 Weil et a l. 26( -327 HENRY R. JILES, Primary Examiner C. M. S. JAISLE, Assistant Examiner 

